Combinations of active ingredients with insecticidal and acaricidal properties

ABSTRACT

The novel active compound combinations of certain cyclic ketoenols and the active compounds (1) to (29) listed in the description have very good insecticidal and acaricidal properties.

[0001] The present invention relates to novel active compoundcombinations comprising known cyclic ketoenols on the one hand and otherknown insecticidally active compounds on the other hand and which arehighly suitable for controlling animal pests such as insects andundesired acarids.

[0002] It is already known that certain cyclic ketoenols haveinsecticidal and acaricidal properties (EP-A-528 156). Further ketoenolshaving insecticidal and acaricidal properties are described in WO95/01971, EP-A-647 637, WO 96/16061, WO 96/20196, WO 96/25395, WO96/35664, WO 97/02243, WO 97/01535, WO 97/36868, WO 97/43275, WO98/05638, WO 98/06721, WO 99/16748, WO 99/43649, WO 99/48869 and WO99/55673. The activity of these substances is good; however, at lowapplication rates it is sometimes unsatisfactory.

[0003] Furthermore, it is already known that numerous heterocycles,organotin compounds, benzoylureas and pyrethroids have insecticidal andacaricidal properties (cf. WO 93-22 297, WO 93-10 083, DE-A 2 641 343,EP-A-347 488, EP-A-210 487, U.S. Pat. No. 3,264,177 and EP-A-234 045).However, the activity of these substances is not always satisfactory.

[0004] in which

[0005] X represents C₁-C₆-alkyl, halogen, C₁-C₆-alkoxy orC₁-C₃-halogenoalkyl,

[0006] Y represents hydrogen, C₁-C₆-alkyl, halogen, C₁-C₆-alkoxy orC₁-C₃-halogenoalkyl,

[0007] Z represents C₁-C₆-alkyl, halogen or C₁-C₆-alkoxy,

[0008] n represents a number from 0 to 3,

[0009] A represents hydrogen or in each case optionallyhalogen-substituted straight-chain or branched C₁-C₁₂-alkyl,C₃-C₈-alkenyl, C₃-C₈-alkinyl, C₁-C₁₀-alkoxy-C₂-C₈-alkyl,C₁-C₈-polyalkoxy-C₂-C₈-alkyl, C₁-C₁₀-alkylthio-C₂-C₈-alkyl or cycloalkylhaving 3-8 ring atoms which may be interrupted by oxygen and/or sulphurand represents in each case optionally halogen-, C₁-C₆-alkyl-,C₁-C₆-halogenoalkyl-, C₁-C₆-alkoxy-, C₁-C₆-halogenoalkoxy- ornitro-substituted phenyl or phenyl-C₁-C₆-alkyl,

[0010] B represents hydrogen, C₁-C₆-alkyl or C₁-C₆-alkoxy-C₂-C₄-alkyl

[0011] or in which

[0012] A and B together with the carbon atom to which they are attachedform a saturated or unsaturated 3- to 8-membered ring which isoptionally interrupted by oxygen and/or sulphur and optionallysubstituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy, C₁-C₄-halogenoalkyl,C₁-C₄-halogenoalkoxy, C₁-C₄-alkylthio or optionally substituted phenylor is optionally benzo-fused,

[0013] G represents hydrogen (a) or represents a group

[0014]  in which

[0015] R¹ represents in each case optionally halogen-substitutedC₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₂-C₈-alkyl,C₁-C₈-alkylthio-C₂-C₈-alkyl, C₁-C₈-polyalkoxy-C₂-C₈-alkyl or cycloalkylhaving 3-8 ring atoms which may be interrupted by oxygen and/or sulphuratoms,

[0016] represents optionally halogen-, nitro-, C₁-C₆-alkyl-,C₁-C₆-alkoxy-, C₁-C₆-halogenoalkyl- or C₁-C₆-halogenoalkoxy-substitutedphenyl,

[0017] represents optionally halogen-, C₁-C₆-alkyl-, C₁-C₆-alkoxy-,C₁-C₆-halogenoalkyl- or C₁-C₆-halogenoalkoxy-substitutedphenyl-C₁-C₆-alkyl,

[0018] represents in each case optionally halogen- and/orC₁-C₆-alkyl-substituted pyridyl, pyrimidyl, thiazolyl or pyrazolyl,

[0019] represents optionally halogen- and/or C₁-C₆-alkyl-substitutedphenoxy-C₁-C₆-alkyl,

[0020] R² represents in each case optionally halogen-substitutedC₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₂-C₈-alkyl orC₁-C₈-polyalkoxy-C₂-C₈-alkyl,

[0021] represents in each case optionally halogen-, nitro-,C₁-C₆-alkyl-, C₁-C₆-alkoxy- or C₁-C₆-halogenoalkyl-substituted phenyl orbenzyl,

[0022] R³ represents optionally halogen-substituted C₁-C₈-alkyl,represents in each case optionally C₁-C₄-alkyl-, halogen-,C₁-C₄-halogenoalkyl-, C₁-C₄-alkoxy-, C₁-C₄-halogenoalkoxy-, nitro- orcyano-substituted phenyl or benzyl,

[0023] R⁴ and R⁵ independently of one another represent in each caseoptionally halogen-substituted C₁-C₈-alkyl, C₁-C₈-alkoxy,C₁-C₈-alkylamino, di-(C₁-C₈)-alkyl-amino, C₁-C₈-alkylthio,C₂-C₅-alkenylthio, C₂-C₅-alkinylthio or C₃-C₇-cycloalkylthio, representin each case optionally halogen-, nitro-, cyano-, C₁-C₄-alkoxy-,C₁-C₄-halogenoalkoxy-, C₁-C₄-alkylthio-, C₁-C₄-halogeno-alkylthio-,C₁-C₄-alkyl- or C₁-C₄-halogenoalkyl-substituted phenyl, phenoxy orphenylthio,

[0024] R⁶ and R⁷ independently of one another represent in each caseoptionally halogen-substituted C₁-C₁₀-alkyl, C₁-C₁₀-alkoxy,C₃-C₈-alkenyl or C₁-C₈-alkoxy-C₁-C₈-alkyl, represent optionallyhalogen-, C₁-C₆-halogenoalkyl-, C₁-C₆-alkyl- or C₁-C₆-alkoxy-substitutedphenyl, represent optionally halogen-, C₁-C₆-alkyl-,C₁-C₆-halogenoalkyl- or C₁-C₆-alkoxy-substituted benzyl or togetherrepresent a 5- or 6-membered ring which is optionally interrupted byoxygen or sulphur and which may optionally be substituted byC₁-C₆-alkyl,

[0025] and bioactive compounds, preferably

[0026] (1) the phenylhydrazine derivative of the formula

[0027]  (bifenazate)

[0028] known from WO 93/10 083 and/or

[0029] (2) the macrolide with the common name

[0030]  abamectin (III)

[0031] known from DE-A-27 17 040 and/or

[0032] (3) the naphthalenedione derivative of the formula

[0033]  (acequinocyl)

[0034] known from DE-A-26 41 343 and/or

[0035] (4) the pyrrole derivative of the formula

[0036]  (chlorfenapyr)

[0037] known from EP-A-347 488 and/or

[0038] (5) the thiourea derivative of the formula

[0039]  (diafenthiuron)

[0040] known from EP-A-210 487 and/or

[0041] (6) the oxazoline derivative of the formula

[0042]  (etoxazole)

[0043] known from WO 93/22 297 and/or

[0044] (7) an organotin derivative of the formula

[0045]  (VIIIa=azocyclotin),

[0046] known from The Pesticide Manual, 9th edition, p.48 or

[0047] R represents —OH

[0048]  (VIIIb=cyhexatin),

[0049] known from U.S. Pat. No. 3,264,177 and/or

[0050] (8) the pyrazole derivative of the formula

[0051]  (tebufenpyrad)

[0052] known from EP-A-289 879 and/or

[0053] (9) the pyrazole derivative of the formula

[0054]  (fenpyroximate)

[0055] known from EP-A-234 045 and/or

[0056] (10) the pyridazinone derivative of the formula

[0057]  (pyridaben)

[0058] known from EP-A-134 439 and/or

[0059] (11) the benzoylurea of the formula

[0060]  (flufenoxuron)

[0061] known from EP-A- 161 019 and/or

[0062] (12) the pyrethroid of the formula

[0063]  (bifenthrin)

[0064] known from EP-A-049 977 and/or

[0065] (13) the tetrazine derivative of the formula

[0066]  (clofentezine)

[0067] known from EP-A-005 912 and/or

[0068] (14) the organotin derivative of the formula

[0069]  (fenbutatin oxide)

[0070] known from DE-A-2 115 666 and/or

[0071] (15) the sulphenamide of the formula

[0072]  (tolylfluanid)

[0073] known from The Pesticide Manual, 11th edition, 1997, page 1208and/or

[0074] (16) the pyrimidyl phenol ethers

[0075] R=Cl (XVII);(4-[(4-chloro-α,α,α-trifluoro-3-tolyl)oxy]-6-[(α,α,α-4-tetrafluoro-3-tolyl)oxy]-pyrimidine)

[0076] R=NO₂ (XVIII);4-[(4-chloro-α,α,α-trifluoro-3-tolyl)oxy]-6-[(α,α,α-trifluoro-4-nitro-3-tolyl)oxy]-pyrimidine

[0077] R=Br (XIX);4-[(4-chloro-α,α,α-trifluoro-3-tolyl)oxy]-6-[(α,α,α-tri-fluoro-4-bromo-3-tolyl)oxy]-pyrimidine

[0078] known from WO 94/02 470, EP-A-883 991 and/or

[0079] (17) the macrolide of the formula

[0080]  (spinosad) a mixture preferably comprising

[0081] 85% spinosyn A R=H

[0082] 15% spinosyn B R=CH₃

[0083] known from EP-A-375 316 and/or

[0084] (18) ivermectin (XXI)

[0085] known from EP-A-001 689 and/or

[0086] (19) milbemectin (XXII)

[0087] known from The Pesticide Manual, 11th edition, 1997, p. 846and/or

[0088] (20) endosulfan (XXIII)

[0089] known from DE-A-1 015 797 and/or

[0090] (21) fenazaquin (XXIV)

[0091] known from EP-A-326 329 and/or

[0092] (22) pyrimidifen (XXV)

[0093] known from EP-A-196 524 and/or

[0094] (23) triarathen (XXVI)

[0095] known from DE-A-2 724 494 and/or

[0096] (24) tetradifon (XXVII)

[0097] known from U.S. Pat. No. 2,812,281 and/or

[0098] (25) propargit (XXVIII)

[0099] known from U.S. Pat. No. 3,272,854 and/or

[0100] (26) hexythiazox (XXIX)

[0101] known from DE-A-3 037 105 and/or

[0102] (27) bromopropylate (XXX)

[0103] known from U.S. Pat. No. 3,784,696 and/or

[0104] (28) dicofol (XXXI)

[0105] known from U.S. Pat. No. 2,812,280 and/or

[0106] (29) chinomethionat (XXXII)

[0107] known from DE-A-1 100 372

[0108] have very good insecticidal and acaricidal properties.

[0109] Surprisingly, the insecticidal and acaricidal action of theactive compound combinations according to the invention considerablyexceeds the total of the actions of the individual active compounds. Atrue synergistic effect which could not have been predicted thereforeexists, not just a complementation of action.

[0110] The active compound combinations according to the inventioncomprise, in addition to at least one active compound of the formula(I), at least one active compound of compounds 1 to 29.

[0111] Preference is given to active compound combinations comprisingcompounds of the formula (I)

[0112] in which

[0113] X represents C₁-C₄-alkyl, halogen, C₁-C₄-alkoxy orC₁-C₂-halogenoalkyl,

[0114] Y represents hydrogen, C₁-C₄-alkyl, halogen, C₁-C₄-alkoxy orC₁-C₂-halogenoalkyl,

[0115] Z represents C₁-C₄-alkyl, halogen or C₁-C₄-alkoxy,

[0116] n represents 0 or 1,

[0117] A and B together with the carbon atom to which they are attachedform a saturated, optionally C₁-C₄-alkyl- or C₁-C₄-alkoxy-substituted 5-or 6-membered ring,

[0118] G represents hydrogen (a) or represents the groups

[0119]  in which

[0120] R¹ represents in each case optionally halogen-substitutedC₁-C₁₆-alkyl, C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₂-C₆-alkyl or cycloalkylhaving 3-7 ring, atoms which may be interrupted by 1 or 2 oxygen and/orsulphur atoms,

[0121] represents optionally halogen-, nitro-, C₁-C₄-alkyl-,C₁-C₄-alkoxy-, C₁-C₃-halogenoalkyl- or C₁-C₃-halogenoalkoxy-substitutedphenyl.

[0122] R² represents in each case optionally halogen-substitutedC₁-C₁₆-alkyl, C₂-C₁₆-alkenyl or C₁-C₆-alkoxy-C₂-C₆-alkyl,

[0123] represents in each case optionally halogen-, nitro-,C₁-C₄-alkyl-, C₁-C₄-alkoxy- or C₁-C₄-halogenoalkyl-substituted phenyl orbenzyl,

[0124] and at least one active compound of compounds 1 to 29.

[0125] Particular preference is given to active compound combinationscomprising the dihydrofuranone derivative of the formula (I-b-1)

[0126] and at least one active compound of compounds 1 to 29.

[0127] In addition, the active compound combinations may also compriseother fungicidally, acaricidally or insecticidally active componentswhich may be admixed.

[0128] If the active compounds are present in the active compoundcombinations according to the invention in certain weight ratios, thesynergistic effect is particularly pronounced. However, the weightratios of the active compounds in the active compound combinations maybe varied within a relatively wide range. In general, the combinationsaccording to the invention comprise active compounds of the formula (I)and the co-components in the preferred and particularly preferred mixingratios indicated in the table below:

[0129] the mixing ratios are based on weight ratios. The ratio is to beunderstood as meaning active compound of the formula (I): co-componentParticularly Preferred preferred Co-component mixing ratio mixing ratiobifenazate  5:1 to 1:20  1:1 to 1:10 abamectin 50:1 to 1:5 10:1 to 1:1acequinocyl 10:1 to 1:10  5:1 to 1:5 chlorfenapyr 10:1 to 1:10  5:1 to1:5 diafenthiuron 10:1 to 1:10  5:1 to 1:5 etoxazole 20:1 to 1:5 10:1 to1:2 azocyclotin 10:1 to 1:10  5:1 to 1:5 cyhexatin 10:1 to 1:10  5:1 to1:5 tebufenpyrad 20:1 to 1:10 10:1 to 1:5 fenpyroximat 10:1 to 1:10  5:1to 1:5 pyridaben 10:1 to 1:10  5:1 to 1:5 flufenoxuron 10:1 to 1:10  5:1to 1:5 bifenthrin 10:1 to 1:10  5:1 to 1:5 clofentezine 10:1 to 1:10 5:1 to 1:5 fenbutatin oxide 10:1 to 1:10  5:1 to 1:5 tolylfluanid  5:1to 1:50  1:1 to 1:5 pyrimidyl phenol ethers (XVII-XIX) 10:1 to 1:10  5:1to 1:5 spinosad 10:1 to 1:10  5:1 to 1:5 ivermectin 50:1 to 1:5 10:1 to1:1 milbemectin 50:1 to 1:5 10:1 to 1:1 endosulfan 10:1 to 1:10  5:1 to1:5 fenazaquin 10:1 to 1:10  5:1 to 1:5 pyrimidifen 50:1 to 1:5 10:1 to1:1 triarathen  5:1 to 1:20  1:1 to 1:10 tetradifon 10:1 to 1:10  5:1 to1:5 propargit 10.1 to 1:10  5:1 to 1:5 hexythiazox 20:1 to 1:5 10:1 to1:2 bromopropylate 10:1 to 1:10  5:1 to 1:5 dicofol 10:1 to 1:10  5:1 to1:5 chinomethionat 10:1 to 1:10  5:1 to 1:5

[0130] The active compound combinations according to the invention aresuitable for controlling animal pests, preferably arthropods andnematodes, in particular insects and arachnids found in agriculture, inanimal health, in forests, in the protection of stored products andmaterials and in the hygiene sector. They are active against normallysensitive and resistant species, and against all or individualdevelopmental stages. The abovementioned pests include:

[0131] From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare, Porcellio scaber.

[0132] From the order of the Diplopoda, for example, Blaniulusguttulatus.

[0133] From the order of the Chilopoda, for example, Geophiluscarpophagus, Scutigera spp.

[0134] From the order of the Symphyla, for example, Scutigerellaimmaculata.

[0135] From the order of the Thysanura, for example, Lepisma saccharina.

[0136] From the order of the Collembola, for example, Onychiurusarmatus.

[0137] From the order of the Orthoptera, for example, Acheta domesticus,Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp.,Schistocerca gregaria.

[0138] From the order of the Blattaria, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica.

[0139] From the order of the Dermaptera, for example, Forficulaauricularia.

[0140] From the order of the Isoptera, for example, Reticulitermes spp.

[0141] From the order of the Phthiraptera, for example, Pediculushumanus corporis, Haematopinus spp., Linogniathus spp., Trichodectesspp., Damalinia spp.

[0142] From the order of the Thysanoptera, for example, Hercinothripsfemoralis, Thrips tabaci, Thrips palmi, Frankliniella occidentalis.

[0143] From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus, Triatoma spp.

[0144] From the order of the Homoptera, for example, Aleurodesbrassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii,Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi,Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix,Pemphigus spp., Macrosiphum avenae, Myzus spp., Phorodon humuli,Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettixcincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus,Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae,Pseudococcus spp., Psylla spp.

[0145] From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella xylostella, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Mamestra brassicae, Panolisflammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pierisspp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleriamellonella, Tineola bisselliella, Tinea pellionella, Hofmannophilapseudospretella, Cacoecia podana, Capua reticulana, Choristoneurafumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana,Cnaphalocerus spp., Oulema oryzae.

[0146] From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrusoryzophilus.

[0147] From the order of the Hymenoptera, for example, Diprion spp.,Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

[0148] From the order of the Diptera, for example, Aedes spp., Anophelesspp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp.,Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebraspp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae,Tipula paludosa, Hylemyia spp., Liriomyza spp.

[0149] From the order of the Siphonaptera, for example, Xenopsyllacheopis, Ceratophyllus spp.

[0150] From the class of the Arachnida, for example, Scorpio maurus,Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp.,Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp.,Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemusspp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.,Hemitarsonemus spp., Brevipalpus spp.

[0151] The plant-parasitic nematodes include, for example, Pratylenchusspp., Radopholus similis, Ditylenchus dipsaci, Tylenchulussemipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp.,Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.,Bursaphelenchus spp.

[0152] The active compound combinations can be converted into thecustomary formulations such as solutions, emulsions, wettable powders,suspensions, powders, dusts, pastes, soluble powders, granules,suspension-emulsion concentrates, natural and synthetic materialsimpregnated with active compound, and microencapsulations in polymericmaterials.

[0153] These formulations are produced in a known manner, for example bymixing the active compounds with extenders, that is, liquid solventsand/or solid carriers, optionally with the use of surfactants, that is,emulsifiers and/or dispersants, and/or foam formers.

[0154] If the extender used is water, it is also possible, for example,to use organic solvents as cosolvents. The following are essentiallysuitable as liquid solvents: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes and methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample mineral oil fractions, mineral and vegetable oils, alcohols suchas butanol or glycol and their ethers and esters, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents such as dimethylformamide and dimethylsulphoxide, or else water.

[0155] Suitable solid carriers are:

[0156] for example ammonium salts and ground natural minerals such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic materials such ashighly-disperse silica, alumina and silicates; suitable solid carriersfor granules are: for example crushed and fractionated natural rockssuch as calcite, marble, pumice, sepiolite and dolomite, or elsesynthetic granules of inorganic and organic meals, and granules oforganic material such as sawdust, coconut shells, maize cobs and tobaccostalks; suitable emulsifiers and/or foam formers are: for examplenonionic and anionic emulsifiers such as polyoxyethylene fatty acidesters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates,or else protein hydrolysates; suitable dispersants are: for examplelignin-sulphite waste liquors and methylcellulose.

[0157] Tackifiers such as carboxymethylcellulose and natural andsynthetic polymers in the form of powders, granules or latices, such asgum arabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other additives can bemineral and vegetable oils.

[0158] It is possible to use colorants such as inorganic pigments, forexample iron oxide, titanium oxide and Prussian Blue, and organiccolorants such alizarin colorants, azo colorants and metalphthalocyanine colorants, and trace nutrients such as salts of iron,manganese, boron, copper, cobalt, molybdenum and zinc.

[0159] The formulations generally comprise between 0.1 and 95% by weightof active compound, preferably between 0.5 and 90%.

[0160] The active compound combinations according to the invention canbe present in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with other activecompounds, such as insecticides, attractants, sterilants, bactericides,acaricides, nematicides, fungicides, growth-regulating substances orherbicides. The insecticides include, for example, phosphates,carbamates, carboxylates, chlorinated hydrocarbons, phenylureas andsubstances produced by microorganisms.

[0161] Mixtures with other known active compounds such as herbicides orwith fertilizers and growth regulators are also possible.

[0162] When used as insecticides, the active compound combinationsaccording to the invention can furthermore be present in theircommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with synergists. Synergists arecompounds which increase the action of the active compounds, without itbeing necessary for the synergist added to be active itself.

[0163] The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

[0164] The compounds are employed in a customary manner appropriate forthe use forms.

[0165] When used against hygiene pests and stored-product pests, theactive compound combinations are distinguished by an excellent residualaction on wood and clay as well as good stability to alkali on limedsubstrates.

[0166] The active compound combinations according to the invention arenot only active against plant pests, hygiene pests and stored-productpests, but also, in the veterinary medicine sector, against animalparasites (ectoparasites) such as hard ticks, soft ticks, mange mites,harvest mites, flies (stinging and licking), parasitizing fly larvae,lice, hair lice, bird lice and fleas. These parasites include:

[0167] From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.

[0168] From the order of the Mallophagida and the suborders Amblycerinaand Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinotonspp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp., Felicola spp.

[0169] From the order Diptera and the suborders Nematocerina andBrachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanusspp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp.,Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fanniaspp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp.,Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp.,Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.

[0170] From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.

[0171] From the order of the Heteropterida, for example, Cimex spp.,Triatoma spp., Rhodnius spp., Panstrongylus spp.

[0172] From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattela germanica, Supella spp.

[0173] From the subclass of the Acaria (Acarida) and the order of theMeta- and Mesostigmata, for example, Argas spp., Ornithodorus spp.,Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentorspp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssusspp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp.

[0174] From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

[0175] The active compound combinations according to the invention arealso suitable for controlling arthropods which attack agriculturallivestock such as, for example, cattle, sheep, goats, horses, pigs,donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese,honey-bees, other domestic animals such as, for example, dogs, cats,caged birds, aquarium fish and so-called experimental animals such as,for example, hamsters, guinea pigs, rats and mice. By controlling thesearthropods, cases of death and reductions in productivity (for meat,milk, wool, hides, eggs, honey and the like) should be diminished, sothat more economical and simpler animal husbandry is possible by the useof the active compound combinations according to the invention.

[0176] The active compound combinations according to the invention areused in the veterinary sector in a known manner by enteraladministration in the form of, for example, tablets, capsules, potions,drenches, granules, pastes, boluses, the feed-through method,suppositories, by parenteral administration such as, for example, byinjections (intramuscularly, subcutaneously, intravenously,intraperitoneally and the like), implants, by nasal administration, bydermal administration in the form of, for example, immersing or dipping,spraying, pouring-on, spotting-on, washing, dusting, and with the aid ofactive-compound-comprising moulded articles such as collars, ear tags,tail tags, limb bands, halters, marking devices and the like.

[0177] When used for cattle, poultry, domestic animals and the like, theactive compound combinations can be applied as formulations (for examplepowders, emulsions, flowables) comprising the active compounds in anamount of 1 to 80% by weight, either directly or after 100- to10,000-fold dilution, or they may be used as a chemical dip.

[0178] Moreover, it has been found that the active compound combinationsaccording to the invention show a potent insecticidal action againstinsects which destroy industrial materials.

[0179] The following insects may be mentioned by way of example and withpreference, but not by way of limitation:

[0180] Beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobiumpunctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobiumpertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctusafricanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens,Trogoxylon aequale, Minthes rugicollis, Xyleborus spec., Tryptodendronspec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus,Sinoxylon spec., Dinoderus minutus.

[0181] Dermapterans such as Sirex juvencus, Urocerus gigas, Urocerusgigas taignus, Urocerus augur.

[0182] Termites such as Kalotermes flavicollis, Cryptotermes brevis,Heterotermes indicola, Reticulitermes flavipes, Reticulitermessantonensis, Reticulitermes lucifugus, Mastotermes darwiniensis,Zootermopsis nevadensis, Coptotermes formosanus.

[0183] Bristle-tails such as Lepisma saccharina.

[0184] Industrial materials in the present context are understood asmeaning non-living materials such as, preferably, polymers, adhesives,glues, paper and board, leather, wood, timber products and paints.

[0185] The material which is to be protected from insect attack is veryespecially preferably wood and timber products.

[0186] Wood and timber products which can be protected by thecomposition according to the invention, or mixtures comprising it, areto be understood as meaning, for example:

[0187] Construction timber, wooden beams, railway sleepers, bridgecomponents, jetties, vehicles made of wood, boxes, pallets, containers,telephone poles, wood lagging, windows and doors made of wood, plywood,chipboard, joinery, or timber products which quite generally are used inhouse construction or building joinery.

[0188] The active compound combinations can be used as such, in the formof concentrates or generally customary formulations such as powders,granules, solutions, suspensions, emulsions or pastes.

[0189] The abovementioned formulations can be prepared in a manner knownper se, for example by mixing the active compounds with at least onesolvent or diluent, emulsifier, dispersant and/or binder or fixative,water repellant, if desired desiccants and UV stabilizers, and ifdesired colorants and pigments and other processing auxiliaries.

[0190] The insecticidal compositions or concentrates used for protectingwood and timber products comprise the active compound according to theinvention in a concentration of 0.0001 to 95% by weight, in particular0.001 to 60% by weight.

[0191] The amount of composition or concentrate employed depends on thespecies and the abundance of the insects and on the medium. The optimalquantity to be employed can be determined in each case by test seriesupon application. In general, however, it will suffice to employ 0.0001to 20% by weight, preferably 0.001 to 10% by weight, of the activecompound, based on the material to be protected.

[0192] A suitable solvent and/or diluent is an organochemical solvent orsolvent mixture and/or an oily or oil-type organochemical solvent orsolvent mixture of low volatility and/or a polar organochemical solventor solvent mixture and/or water and, if appropriate, an emulsifierand/or wetter.

[0193] Organochemical solvents which are preferably employed are oily oroil-type solvents with an evaporation number of above 35 and a flashpoint of above 30° C., preferably above 45° C., Such oily and oil-typesolvents which are insoluble in water and of low volatility and whichare used are suitable mineral oils or their aromatic fractions ormineral-oil-containing solvent mixtures, preferably white spirit,petroleum and/or alkylbenzene.

[0194] Mineral oils with a boiling range of 170 to 220° C., white spiritwith a boiling range of 170 to 220° C., spindle oil with a boiling rangeof 250 to 350° C., petroleum and aromatics with a boiling range of 160to 280° C., oil of terpentine, and the like are advantageously used.

[0195] In a preferred embodiment, liquid aliphatic hydrocarbons with aboiling range of 180 to 210° C. or high-boiling mixtures of aromatic andaliphatic hydrocarbons with a boiling range of 180 to 220° C. and/orspindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene are used.

[0196] The organic oily or oil-type solvents of low volatility and withan evaporation number of above 35 and a flash point of above 30° C.,preferably above 45° C., can be replaced in part by organochemicalsolvents of high or medium volatility, with the proviso that the solventmixture also has an evaporation number of above 35 and a flash point ofabove 30° C., preferably above 45° C., and that the mixture is solubleor emulsifiable in this solvent mixture.

[0197] In a preferred embodiment, some of the organochemical solvent orsolvent mixture or an aliphatic polar organochemical solvent or solventmixture is replaced. Aliphatic organochemical solvents which containhydroxyl and/or ester and/or ether groups are preferably used, such as,for example, glycol ethers, esters or the like.

[0198] Organochemical binders used for the purposes of the presentinvention are the synthetic resins and/or binding drying oils which areknown per se and which can be diluted in water and/or dissolved ordispersed or emulsified in the organochemical solvents employed, inparticular binders composed of, or comprising, an acrylate resin, avinyl resin, for example polyvinyl acetate, polyester resin,polycondensation or polyaddition resin, polyurethane resin, alkyd resinor modified alkyd resin, phenol resin, hydrocarbon resin such asindene/coumarone resin, silicone resin, drying vegetable and/or dryingoils and/or physically drying binders based on a natural and/orsynthetic resin.

[0199] The synthetic resin employed as binder can be employed in theform of an emulsion, dispersion or solution. Bitumen or bituminoussubstances may also be used as binders, in amounts of up to 10% byweight. In addition, colorants, pigments, water repellants,odour-masking agents, and inhibitors or anticorrosive agents and thelike, all of which are known per se, can be employed.

[0200] In accordance with the invention, the composition or theconcentrate preferably comprises, as organochemical binders, at leastone alkyd resin or modified alkyd resin and/or a drying vegetable oil.Alkyd resins which are preferably used in accordance with the inventionare those with an oil content of over 45% by weight, preferably 50 to68% by weight.

[0201] Some or all of the abovementioned binder can be replaced by afixative (mixture) or plasticizer (mixture). These additives areintended to prevent volatilization of the active compounds, and alsocrystallization or precipitation. They preferably replace 0.01 to 30% ofthe binder (based on 100% of binder employed).

[0202] The plasticizers are from the chemical classes of the phthalicesters, such as dibutyl phthalate, dioctyl phthalate or benzyl butylphthalate, phosphoric esters such as tributyl phosphate, adipic esterssuch as di-(2-ethylhexyl)-adipate, stearates such as butyl stearate oramyl stearate, oleates such as butyl oleate, glycerol ethers orhigher-molecular-weight glycol ethers, glycerol esters andp-toluenesulphonic esters.

[0203] Fixatives are based chemically on polyvinyl alkyl ethers such as,for example, polyvinyl methyl ether, or ketones such as benzophenone andethylenebenzophenone.

[0204] Other suitable solvents or diluents are, in particular, water, ifappropriate as a mixture with one or more of the abovementionedorganochemical solvents or diluents, emulsifiers and dispersants.

[0205] Particularly effective timber protection is achieved byindustrial-scale impregnating processes, for example the vacuum,double-vacuum or pressure processes.

[0206] The active compound combinations according to the invention canat the same time be employed for protecting objects which come intocontact with saltwater or brackish water, such as hulls, screens, nets,buildings, moorings and signalling systems, against fouling.

[0207] Fouling by sessile Oligochaeta, such as Serpulidae, and by shellsand species from the Ledamorpha group (goose barnacles), such as variousLepas and Scalpellum species, or by species from the Balanomorpha group(acorn barnacles), such as Balanus or Pollicipes species, increases thefrictional drag of ships and, as a consequence, leads to a markedincrease in operation costs owing to higher energy consumption andadditionally frequent residence in the dry dock.

[0208] Apart from fouling by algae, for example Ectocarpus sp. andCeramium sp., fouling by sessile Entomostraka groups, which come underthe generic term Cirripedia (cirriped crustaceans), is of particularimportance.

[0209] Surprisingly, it has now been found that the active compoundcombinations according to the invention have an outstanding antifoulingaction.

[0210] Using the active compound combinations according to theinvention, allows the use of heavy metals such as, for example, inbis(trialkyltin) sulphides, tri-n-butyltin laurate, tri-n-butyltinchloride, copper(I) oxide, triethyltin chloride,tri-n-butyl(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenumdisulphide, antimony oxide, polymeric butyl titanate,phenyl-(bispyridine)-bismuth chloride, tri-n-butyltin fluoride,manganese ethylenebisthiocarbamate, zinc dimethyldithiocarbamate, zincethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol1-oxide, bisdimethyldithiocarbamoylzinc ethylene-bisthiocarbamate, zincoxide, copper(I) ethylene-bisdithiocarbamate, copper thiocyanate, coppernaphthenate and tributyltin halides to be dispensed with, or theconcentration of these compounds to be substantially reduced.

[0211] If appropriate, the ready-to-use antifouling paints canadditionally comprise other active compounds, preferably algicides,fungicides, herbicides, molluscicides, or other antifouling activecompounds.

[0212] Preferably suitable components in combinations with theantifouling compositions according to the invention are:

[0213] algicides such as2-tert-butylamino-4-cyclopropylamino-6-methylthio- 1,3,5-triazine,dichlorophen, diuron, endothal, fentine acetate, isoproturon,methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;

[0214] fungicides such as benzo[b]thiophenecarboxylic acidcyclohexylamide S,S-dioxide, dichlofluanid, fluor-folpet,3-iodo-2-propinyl butylcarbamate, tolylfluanid and azoles such asazaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole,propiconazole and tebuconazole;

[0215] molluscicides such as fentin acetate, metaldehyde, methiocarb,niclosamid, thiodicarb and trimethacarb;

[0216] or conventional antifouling active compounds such as4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatrylsulphone, 2-(N,N-di-methylthiocarbamoylthio)-5-nitrothiazyl, potassium,copper, sodium and zinc salts of 2-pyridinethiol 1-oxide,pyridine-triphenylborane, tetrabutyldistannoxane,2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine,2,4,5,6-tetrachloroisophthalonitrile, tetra-methylthiuram disulphide and2,4,6-trichlorophenylmaleiimide.

[0217] The antifouling compositions used comprise the active compoundcombinations according to the invention in a concentration of 0.001 to50% by weight, in particular 0.01 to 20% by weight.

[0218] Moreover, the antifouling compositions according to the inventioncomprise the customary components such as, for example, those describedin Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, AntifoulingMarine Coatings, Noyes, Park Ridge, 1973.

[0219] Besides the algicidal, fungicidal, molluscicidal active compoundsand insecticidal active compounds according to the invention,antifouling paints comprise, in particular, binders.

[0220] Examples of recognized binders are polyvinyl chloride in asolvent system, chlorinated rubber in a solvent system, acrylic resinsin a solvent system, in particular in an aqueous system, vinylchloride/vinyl acetate copolymer systems in the form of aqueousdispersions or in the form of organic solvent systems,butadiene/styrene/acrylonitrile rubbers, drying oils such as linseedoil, resin esters or modified hardened resins in combination with tar orbitumens, asphalt and epoxy compounds, small amounts of chlorine rubber,chlorinated polypropylene and vinyl resins.

[0221] If appropriate, paints also comprise inorganic pigments, organicpigments or colorants which are preferably insoluble in saltwater.Paints may furthermore comprise materials such as colophonium to allowcontrolled release of the active compounds. Furthermore, the paints maycomprise plasticizers, modifiers which affect the rheological propertiesand other conventional constituents. The compounds according to theinvention or the abovementioned mixtures may also be incorporated intoself-polishing antifouling systems.

[0222] The active compound combinations are also suitable forcontrolling animal pests, in particular insects, arachnids and mites,which are found in enclosed spaces such as, for example, dwellings,factory halls, offices, vehicle cabins and the like. They can beemployed in domestic insecticide products for controlling these pests.They are active against sensitive and resistant species and against alldevelopmental stages. These pests include:

[0223] From the order of the Scorpionidea, for example, Buthusoccitanus.

[0224] From the order of the Acarina, for example, Argas persicus, Argasreflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus,Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi,Neutrombicula autumnalis, Dermatophagoides pteronissimus,Dermatophagoides forinae.

[0225] From the order of the Araneae, for example, Aviculariidae,Araneidae.

[0226] From the order of the Opiliones, for example, Pseudoscorpioneschelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.

[0227] From the order of the Isopoda, for example, Oniscus asellus,Porcellio scaber.

[0228] From the order of the Diplopoda, for example, Blaniulusguttulatus, Polydesmus spp.

[0229] From the order of the Chilopoda, for example, Geophilus spp.

[0230] From the order of the Zygentoma, for example, Ctenolepisma spp.,Lepisma saccharina, Lepismodes inquilinus.

[0231] From the order of the Blattaria, for example, Blatta orientalies,Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchloraspp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana,Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.

[0232] From the order of the Saltatoria, for example, Acheta domesticus.

[0233] From the order of the Dermaptera, for example, Forficulaauricularia.

[0234] From the order of the Isoptera, for example, Kalotermes spp.,Reticulitermes spp.

[0235] From the order of the Psocoptera, for example, Lepinatus spp.,Liposcelis spp.

[0236] From the order of the Coleptera, for example, Anthrenus spp.,Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinusspp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae,Sitophilus zeamais, Stegobium paniceum.

[0237] From the order of the Diptera, for example, Aedes aegypti, Aedesalbopictus, Aedes taeniorhynchus, Anopheles spp., Calliphoraerythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culexpipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Muscadomestica, Phlebotomus spp., Sarcophaga carnaria, Simulium spp.,Stomoxys calcitrans, Tipula paludosa.

[0238] From the order of the Lepidoptera, for example, Achroia grisella,Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tineapellionella, Tineola bisselliella.

[0239] From the order of the Siphonaptera, for example, Ctenocephalidescanis, Ctenocephalides felis, Pulex irritans, Tunga penetrans,Xenopsylla cheopis.

[0240] From the order of the Hymenoptera, for example, Camponotusherculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus,Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.

[0241] From the order of the Anoplura, for example, Pediculus humanuscapitis, Pediculus humanus corporis, Phthirus pubis.

[0242] From the order of the Heteroptera for example, Cimex hemipterus,Cimex lectularius, Rhodinus prolixus, Triatoma infestans.

[0243] They are used as aerosols, pressure-free spray products, forexample pump and atomizer sprays, automatic fogging systems, foggers,foams, gels, evaporator products with evaporator tablets made ofcellulose or polymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free, or passive, evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations.

[0244] All plants and plant parts can be treated in accordance with theinvention. Plants are to be understood as meaning in the present contextall plants and plant populations such as desired and undesired wildplants or crop plants (inclusive of naturally occurring crop plants).Crop plants can be plants which can be obtained by conventional plantbreeding and optimization methods or by biotechnological and geneticalengineering or by combinations of these methods, inclusive of thetransgenic plants and inclusive of the plant varieties protectable ornot protectable by plant breeders' rights, such as shoot, leaf, flowerand root, examples which may be mentioned being leaves, needles, stalks,stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes.The plant parts also include harvested material, and vegetative andgenerative propagation material, for example cuttings, tubers, rhizomes,offsets and seeds.

[0245] Treatment according to the invention of the plants and plantparts with the active compounds is carried out directly or by allowingthe compounds to act on the surroundings, environment or storage spaceby the customary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on and, in the case ofpropagation material, in particular in the case of seed, also byapplying one or more coats.

[0246] As already mentioned above, it is possible to treat all plantsand their parts according to the invention. In a preferred embodiment,wild plant species and plant varieties, or those obtained byconventional biological breeding, such as crossing or protoplast fusion,and parts thereof, are treated. In a further preferred embodiment,transgenic plants and plant varieties obtained by genetical engineering,if appropriate in combination with conventional methods (GeneticModified Organisms), and parts thereof are treated. The term “parts” or“parts of plants” or “plant parts” has been explained above.

[0247] Particularly preferably, plants of the plant varieties which arein each case commercially available or in use are treated according tothe invention.

[0248] Depending on the plant species or plant varieties, their locationand growth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions which can be used accordingto the invention, better plant growth, increased tolerance to high orlow temperatures, increased tolerance to drought or to water or soilsalt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, better quality and/or ahigher nutritional value of the harvested products, better storagestability and/or processability of the harvested products are possiblewhich exceed the effects which were actually to be expected.

[0249] The transgenic plants or plant varieties (i.e. those obtained bygenetical engineering) which are preferred and to be treated accordingto the invention include all plants which, in the genetic modification,received genetic material which imparts particularly advantageous usefulproperties (“traits”) to these plants. Examples of such properties arebetter plant growth, increased tolerance to high or low temperatures,increased tolerance to drought or to water or soil salt content,increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products. Further andparticularly emphasized examples of such properties are a better defenceof the plants against animal and microbial pests, such as againstinsects, mites, phytopathogenic fungi, bacteria and/or viruses, and alsoincreased tolerance of the plants to certain herbicidally activecompounds. Examples of transgenic plants which may be mentioned are theimportant crop plants, such as cereals (wheat, rice), maize, soya beans,potatoes, cotton, oilseed rape and also fruit plants (with the fruitsapples, pears, citrus fruits and grapevines), and particular emphasis isgiven to maize, soya beans, potatoes, cotton and oilseed rape. Traitsthat are particularly emphasized are increased defence of the plantsagainst insects by toxins formed in the plants, in particular thoseformed by the genetic material from Bacillus thuringiensis (for exampleby the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2,Cry9c Cry2Ab, Cry3Bb and CryIF and also combinations thereof)(hereinbelow referred to as “Bt plants”). Traits that are furthermoreparticularly emphasized are the increased tolerance of the plants tocertain herbicidally active compounds, for example imidazolinones,sulphonylureas, glyphosate or phosphinotricin (for example the “PAT”gene). The genes which impart the desired traits in question can also bepresent in combination with one another in the transgenic plants.Examples of “Bt plants” which may be mentioned are maize varieties,cotton varieties, soya bean varieties and potato varieties which aresold under the trade names YIELD GARD® (for example maize, cotton, soyabeans), KnockOut® (for example maize), StarLink® (for example maize),Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples ofherbicide-tolerant plants which may be mentioned are maize varieties,cotton varieties and soya bean varieties which are sold under the tradenames Roundup Ready® (tolerance to glyphosate, for example maize,cotton, soya bean), Liberty Link® (tolerance to phosphinotricin, forexample oilseed rape), IMI® (tolerance to imidazolinones) and STS®(tolerance to sulphonylurea, for example maize). Herbicide-resistantplants (plants bred in a conventional manner for herbicide tolerance)which may be mentioned include the varieties sold under the nameClearfield® (for example maize). Of course, these statements also applyto plant varieties having these or still to be developed genetic traits,which plants will be developed and/or marketed in the future.

[0250] The plants listed can be treated according to the invention in aparticularly advantageous manner with the active compound mixturesaccording to the invention. The preferred ranges stated above for themixtures also apply to the treatment of these plants. Particularemphasis is given to the treatment of plants with the mixturesspecifically mentioned in the present text.

[0251] The good insecticidal and acaricidal action of the activecompound combinations according to the invention can be seen from theexamples which follow. While the individual active compounds showweaknesses in their action, the combinations show an action whichexceeds a simple sum of actions.

[0252] A synergistic effect in insecticides and acaricides is alwayspresent when the action of the active compound combinations exceeds thetotal of the actions of the active compounds when applied individually.

[0253] The expected action for a given combination of two activecompounds can be calculated as follows, using the formula of S. R.Colby, Weeds 15 (1967), 20-22:

[0254] If

[0255] X is the kill rate, expressed as % of the untreated control, whenemploying active compound A at an application rate of m g/ha or in aconcentration of m ppm,

[0256] Y is the kill rate, expressed as % of the untreated control, whenemploying active compound B at an application rate of n g/ha or in aconcentration of n ppm and

[0257] E is the kill rate, expressed as % of the untreated control, whenemploying active compounds A and B at application rates of m and n g/haor in a concentration of m and n ppm,

[0258] then $E = {X + Y - \frac{X \cdot Y}{100}}$

[0259] If the actual insecticidal kill rate exceeds the calculatedvalue, the action of the combination is superadditive, i.e. asynergistic effect is present. In this case, the actually observed killrate must exceed the value calculated using the above formula for theexpected kill rate (E).

[0260] After the desired period of time, the kill in % is determined.100% means that all animals have been killed; 0% means that none of theanimals have been killed.

EXAMPLE

[0261] Critical Concentration Test/soil Insects—Treatment of TransgenicPlants

[0262] Test insect: Diabrotica balteata—larvae in soil

[0263] Solvent: 7 parts by weight of acetone

[0264] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0265] To produce a suitable preparation of active compound, 1 part byweight of active compound is mixed with the stated amount of solvent,the stated amount of emulsifier is added and the concentrate is dilutedwith water to the desired concentration.

[0266] The preparation of active compound is poured onto the soil. Here,the concentration of the active compound in the preparation is virtuallyirrelevant, only the amount by weight of active compound per volume unitof soil, which is stated in ppm (mg/l), matters. The soil is filled into0.251 pots and these are allowed to stand at 20° C.

[0267] Immediately after preparation, 5 pre-germinated maize corns ofthe variety YIELD GUARD (trade mark of Monsanto Comp., USA) are placedinto each pot. After 2 days, the test insects in question are placedinto the treated soil. After a further 7 days, the efficacy of theactive compound is determined by counting the maize plants that haveemerged (1 plant=20% efficacy).

EXAMPLE

[0268] Heliothis Virescens Test—Treatment of Transgenic Plants

[0269] Solvent: 7 parts by weight of acetone

[0270] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0271] To produce a suitable preparation of active compound, 1 part byweight of active compound is mixed with the stated amount of solvent andthe stated amount of emulsifier, and the concentrate is diluted withwater to the desired concentration.

[0272] Soya bean shoots (glycine max) of the variety Roundup Ready(trade mark of Monsanto Comp. USA) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with the tobacco budworm Heliothis virescens while the leavesare still moist.

[0273] After the desired period of time, the kill of the insects isdetermined.

Patent claims
 1. Compositions comprising mixtures of compounds of theformula (I)

in which X represents C₁-C₆-alkyl, halogen, C₁-C₆-alkoxy orC₁-C₃-halogenoalkyl, Y represents hydrogen, C₁-C₆-alkyl, halogen,C₁-C₆-alkoxy or C₁-C₃-halogenoalkyl, Z represents C₁-C₆-alkyl, halogenor C₁-C₆-alkoxy, n represents a number from 0 to 3, A representshydrogen or in each case optionally halogen-substituted straight-chainor branched C₁-C₁₂-alkyl, C₃-C₈-alkenyl, C₃-C₈-alkinyl,C₁-C₁₀-alkoxy-C₂-C₈-alkyl, C₁-C₈-polyalkoxy-C₂-C₈-alkyl,C₁-C₁₀-alkylthio-C₂-C₈-alkyl or cycloalkyl having 3-8 ring atoms whichmay be interrupted by oxygen and/or sulphur and represents in each caseoptionally halogen-, C₁-C₆-alkyl-, C₁-C₆-halogenoalkyl-, C₁-C₆-alkoxy-,C₁-C₆-halogenoalkoxy- or nitro-substituted phenyl or phenyl-C₁-C₆-alkyl, B represents hydrogen, C₁-C₆-alkyl orC₁-C₆-alkoxy-C₂-C₄-alkyl or in which A and B together with the carbonatom to which they are attached form a saturated or unsaturated 3- to8-membered ring which is optionally interrupted by oxygen and/or sulphurand optionally substituted by halogen, C₁-C₆-alkyl, C₁-C₆-alkoxy,C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy, C₁-C₄-alkylthio or optionallysubstituted phenyl or is optionally benzo-fused, G represents hydrogen(a) or represents a group

 in which R¹ represents in each case optionally halogen-substitutedC₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₁-C₈-alkoxy-C₂-C₈-alkyl,C₁-C₈-alkylthio-C₂-C₈-alkyl, C₁-C₈-polyalkoxy-C₂-C₈-alkyl or cycloalkylhaving 3-8 ring atoms which may be interrupted by oxygen and/or sulphuratoms, represents optionally halogen-, nitro-, C₁-C₆-alkyl-,C₁-C₆-alkoxy-, C₁-C₆-halogenoalkyl- or C₁-C₆-halogenoalkoxy-substitutedphenyl, represents optionally halogen-, C₁-C₆-alkyl-, C₁-C₆-alkoxy-,C₁-C₆-halogenoalkyl- or C₁-C₆-halogenoalkoxy-substitutedphenyl-C₁-C₆-alkyl, represents in each case optionally halogen- and/orC₁-C₆-alkyl-substituted pyridyl, pyrimidyl, thiazolyl or pyrazolyl,represents optionally halogen- and/or C₁-C₆-alkyl-substitutedphenoxy-C₁-C₆-alkyl, R² represents in each case optionallyhalogen-substituted C₁-C₂₀-alkyl, C₂-C₂₀-alkenyl,C₁-C₈-alkoxy-C₂-C₈-alkyl or C₁-C₈-polyalkoxy -C₂-C₈-alkyl, represents ineach case optionally halogen-, nitro-, C₁-C₆-alkyl-, C₁-C₆-alkoxy- orC₁-C₆-halogenoalkyl-substituted phenyl or benzyl, R³ representsoptionally halogen-substituted C₁-C₈-alkyl, represents in each caseoptionally C₁-C₄-alkyl-, halogen-, C₁-C₄-halogenoalkyl-, C₁-C₄-alkoxy-,C₁-C₄-halogenoalkoxy-, nitro- or cyano-substituted phenyl or benzyl, R⁴and R⁵ independently of one another represent in each case optionallyhalogen-substituted C₁-C₈-alkyl, C₁-C₈-alkoxy, C₁-C₈-alkylamino,di-(C₁-C₈)-alkylamino, C₁-C₈-alkylthio, C₂-C₅-alkenylthio,C₂-C₅-alkinylthio or C₃-C₇-cycloalkylthio, represent in each caseoptionally halogen-, nitro-, cyano-, C₁-C₄-alkoxy-,C₁-C₄-halogenoalkoxy-, C₁-C₄-alkylthio-, C₁-C₄-halogenoalkylthio-,C₁-C₄-alkyl- or C₁-C₄-halogenoalkyl-substituted phenyl, phenoxy orphenylthio, R⁶ and R⁷ independently of one another represent in eachcase optionally halogen-substituted C₁-C₁₀-alkyl, C₁-C₁₀-alkoxy,C₃-C₈-alkenyl or C₁-C₈-alkoxy-C₁-C₈-alkyl, represent optionallyhalogen-, C₁-C₆-halogenoalkyl-, C₁-C₆-alkyl- or C₁-C₆-alkoxy-substitutedphenyl, represent optionally halogen-, C₁-C₆-alkyl-,C₁-C₆-halogenoalkyl- or C₁-C₆-alkoxy-substituted benzyl or togetherrepresent a 5- or 6-membered ring which is optionally interrupted byoxygen or sulphur and which may optionally be substituted byC₁-C₆-alkyl, and at least one of the compounds below bifenazateabamectin acequinocyl chlorfenapyr diafenthiuron etoxazole azocyclotincyhexatin tebufenpyrad fenpyroximat pyridaben flufenoxuron bifenthrinclofentezine fenbutatin oxide tolylfluanid pyrimidyl phenol ethers(XVII-XIX) spinosad ivermectin milbemectin endosulfan fenazaquinpyrimidifen triarathen tetradifon propargit hexythiazox bromopropylatedicofol chinomethionat
 2. Compositions according to claim 1, comprisingcompounds of the formula (I) in which X represents C₁-C₄-alkyl, halogen,C₁-C₄-alkoxy or C₁-C₂-halogenoalkyl, Y represents hydrogen, C₁-C₄-alkyl,halogen, C₁-C₄-alkoxy or C₁-C₂-halogenoalkyl, Z represents C₁-C₄-alkyl,halogen or C₁-C₄-alkoxy, n represents 0 or 1, A and B together with thecarbon atom to which they are attached form a saturated, optionallyC₁-C₄-alkyl- or C₁-C₄-alkoxy-substituted 5- or 6-membered ring, Grepresents hydrogen (a) or represents the groups —CO—R¹  (b)

 in which R¹ represents in each case optionally halogen-substitutedC₁-C₁₆-alkyl, C₂-C₁₆-alkenyl, C₁-C₆-alkoxy-C₂-C₆-alkyl, or cycloalkylhaving 3-7 ring atoms which may be interrupted by 1 or 2 oxygen and/orsulphur atoms, represents optionally halogen-, nitro-, C₁-C₄-alkyl-,C₁-C₄-alkoxy-, C₁-C₃-halogenoalkyl-, C₁-C₃-halogenoalkoxy-substitutedphenyl; R² represents in each case optionally halogen-substitutedC₁-C₁₆-alkyl, C₂-C₁₆-alkenyl or C₁-C₆-alkoxy-C₂-C₆-alkyl, represents ineach case optionally halogen-, nitro-, C₁-C₄-alkyl-, C₁-C₄-alkoxy- orC₁-C₄-halogenoalkyl-substituted phenyl or benzyl.
 3. Compositionsaccording to claim 1, comprising the compound of the formula (I-b-1)


4. Use of mixtures as defined in claim 1, 2 and 3 for controlling animalpests.
 5. Method for controlling animal pests, characterized in thatmixtures as defined in claim 1, 2 and 3 are allowed to act on animalpests and/or their habitat.
 6. Process for preparing insecticidal andacaricidal compositions, characterized in that mixtures as defined inclaim 1, 2 and 3 are mixed with extenders and/or surfactants.